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Патент USA US3049403

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United States Patent 0 " ICC
2
1
3,049,393
diamine. The nitro derivative obtained is reduced to
beta aminoethyl p-phenylene diamine which is thereafter
-
NITRO PHENYLENEDIAMINE COMPOSITIONS
AND METHOD FOR DYEING ANIMAL FIBERS
acetylated. The triacetyl derivative obtained is nitrated,
John Robert Seemuller, Maisons-La?itte, France, assignor
to Société Anonyme (lite: L’Oreal, Paris, France, a cor
poration of France
a
3,049,393
Patented Aug. 14, 1962
and then deacetylated in order to obtain the desired com
5 pound.
The steps of this synthesis are represented below.
No Drawing. Filed Apr. 12, 1961, Ser. No. 102,102
Claims priority, application France Nov. 29, 1955
11 Claims. (Cl. 8—10)
01
NH-oHr-cHr-NH,
I
The present invention relates to new nitro-aromatic
compounds and their use in dyeing, particularly for dye
ing animal ?bres and more especially dyeing live hair.
Many dyestuffs of the type containing an aromatic nu
cleus having one or more substituted or unsubstituted
amino groups and/or a number of nitro groups have been 15
N0,
NO:
I
()
(n>
employed for dyeing animal ?bres. The conditions which
must be satis?ed in dyeing live hair, which include dyeing
at a temperature which can be withstood by the subject,
minimum toxicity, and effective application to grey, white
or bleached hair, considerably limit the number of dyes 20
—.
which can be so used.
There have already been described and proposed for
NH-O O~CH1
such a use nitro aromatic diamines such as, for example
nitro-p-phenylenediamines in which the amino group meta
to the nitro group, is mono-substituted by a mono- or
poly-hydroxy-alkyl group. However, compounds of this
(III)
25
(IV)
/C O-GH;
N
type in which the substituent on the amino group‘ is a
NH-CHz-CHz-NHI
hydroxy methyl radical, have inadequate stability even
when the hydroxyl group is esteri?ed with an inorganic
acid. The same holds true when the hydroxy-alkyl radical 30
N0:
is heavier, for example, hydroxyethyl or hydroxyiso
propyl.
Introducing hydroxyl groups in these compounds, as
well as esterifying these groups with an inorganic poly
N0’
NH-C O—OH;
NH;
(V)
(VI)
basic acid aims at increasing the Water-solubility of the 35 The method of operation followed and the character
istics of the compounds obtained are as follows:
dyes, which are otherwise sparingly soluble.
The Compound II is prepared by the process of I. P. F.
It is an object of this invention to provide stable nitro
Fourneau and Madame Y. de Lestrange (Bull. Soc. Chim.
phenylene diamine compounds which are particularly suit
1947, page 834).
able for dyeing animal ?bres, and more especially live
REDUCTION OF THE COMPOUND II TO THE
hair, at moderate temperatures. It is a further object to 40
provide compositions containing such compounds.
COMPOUND III
The nitro, ortho and para-phenylenediamine, in which
300 g. of iron powder are introduced into 1200 ml. of
water to which 10 ml. of glacial acetic acid have been
added and the mixture is heated to 85—90° C. 181 g. (1
the nitro group is in a meta position to one of the amino
groups, and in which the amino group remote from the
45 mol.) of Compound II are then gradually added, the tem
nitro is a group which has the general formula
perature being maintained at 90° C. while 55 m]. of
acetic acid are added in the course of the reduction. The
in which R1, R2 and R3 each represent an atom of hydro
reaction is complete within half an hour. The reaction
gen or an alkyl radical having from one to 3 atoms of
product is made alkaline with 4 g. of sodium carbonate
carbon, m represents an integer between 2 and 4 and n 50 and ?ltered hot.
is equal to 0 or 1.
It is unnecessary to isolate Compound III in order to
According to a further feature of the invention a com
effect the acetylation.
position for application to the hair for dyeing same com
ACE'I‘YLATION OF THE COMPOUND III TO THE
prises an alkaline solution of a compound as just de?ned.
COMPOUND IV
According to a still further feature of the invention a 55
Immediately after the ?ltration, 425 g. of acetic an
method of dyeing animal ?bres and more particularly live
hydride
are added to the ?ltrate at 90° C. with vigorous
hair comprises applying thereto an alkaline solution of a
stirring and the mixture is heated for 1 hour at 80-90° C.
compound as just de?ned.
After cooling, 500 g. of crushed ice are added and the
The following examples will serve to illustrate the in
vention but are not to be regarded as limiting it in any 60 mixture is neutralized with 550 ml. of 40% sodium hy
droxide solution, care being taken that the temperature
way:
does not rise above 7° C. The triacetyl derivative IV
EXAMPLE 1
is allowed to crystallize, ?ltered and dried at 65~70° C.
It melts at 191° C. and the yield is 94%. After re
I-Amino-Z-Nitro-lI-?-Aminoethylamino-Benzene
NH—CH;CHzNHg
65
crystallization, the melting point is 195-l96° C.
Analysis:
Element
Calculated
Found
percent ' I percent’;
. N0:
in.
p-Nitrochlorobenzene is ?rst condensed with ethylene
....................................... ..
70 H ....................................... --
60.64
'
60.24
6.85
7.11
15.16
15.15
3,049,393
4
‘ the hydrochloride, which melts at 233—235° C. Yield:
NITRATION OF‘ THE COMPOUND IV
60%.
84 g. of the Compound IV are dissolved in 500 ml. of
While the amine of Formula VIH hydrates readily, the
concentrated sulphuric acid (66° Bé.) and the nitration
hydrochloride prepared as indicated above keeps well.
is effected at 15° C. by pouring in a sulphuric nitric acid
mixture consisting of 66 g. of nitric acid having a density 5 It is dissolved in 800 ml. of water, neutralized with 40%
aqueous sodium hydroxide solution and the precipitated
of 1.38 and 66 g. of concentrated sulphuric acid, the tem
product
is ?ltered and dried in a desiccator for 3 days.
perature being maintained between 20° and 25°C. for
The free amine thus prepared melts at 84-85” C. Yield:
41/: hours. The product is poured on to crushed ice and
80%.
neutralized with 40% aqueous sodium hydroxide solu
Controlled reduction.~—0.l mol. of the Compound VIII
tion, care beaing taken that the temperature does not rise 10
is brought into suspension in 450 ml. of ethyl alcohol
above 40° C. The reaction mixture is extracted with
containing from 8% to 9% of NH3 added. Hydrogen
ethyl acetate. The extract is then distilled to drive off
sulphide gas is then bubbled therethrough. Dissolution
the ethyl acetate and the residue is recrystallized from
of the Compound VIII is complete within 15 minutes
absolute alcohol.
35 g. of the Compound V are thus obtained in the 15 and the solution turns gradually orange, red and dark
brown. The stream of gas is bubbled through for 6
form of lemon-yellow needles melting at 207-208" C.
hours at a temperature of between 30-40“ C.
DEACETYLATION OF THE COMPOUND V
The alco
holic solution is then evaporated to dryness under reduced
The Compound V is re?uxed for an hour and a half
pressure.
with 200 ml. of 50% aqueous sulphuric acid. After 20
The residue is dissolved in 7% hot aqueous hydro
cooling, 600 ml. of ethyl alcohol are added. The mix
chloric acid. The sulphur which has precipitated is
ture is left overnight in a refrigerator, and the crystals
?ltered. The hydrochloride is then neutralized with 40%
formed are then ?ltered. The dark-colored viscous resi
aqueous sodium hydroxide solution. The base precipi
due is warmed, ?ltered through bone-black and returned
tates upon cooling. On successive recrystallizations
into the refrigerator. A further quantity of crystals is 25 from water in the presence of bone-black, red ?akes melt
recovered. The sulphate of the compound of Formula
ing at 135—136° C. are obtained. Yield: 50%.
VI is thus obtained in the form of yellow crystals which
The base, Formula IX, is dried in a desiccator.
decompose at 185° C. The free base is very hygroscopic
Dyeing.—A 1% solution of the Compound IX is pre
and it is preferred to use the sulphate.
pared and made weakly alkaline, and this solution is
Dyeing.—A 2% aqueous solution of 1-amino-2-nitro
applied in the cold to live hair. A golden shade is ob
4-;3~aminoethylamino-benzene sulphate is prepared and 30 tained, which is brighter than that obtained with nitro-o
made alkaline by adding a base, for example ammonia.
phenylenediamine.
This solution is applied in the cold to live hair or sim
ilar ?bres, and a beautiful dark violet shade is obtained.
EXAMPLE 3
1-Amin0-2-Nitr0-4-N-A cetamido-Amino-Benzene
The addition of hydrogen peroxide does not shift the 35
shade.
NH-C Hr-C O-NH:
EXAMPLE 2
1-Nitr0-3-Amin0-4-B-Aminoethylamino-Benzene
.'
NO’
This product is obtained by condensation of ethylene 40
diamine with 1,3-dinitro-4-chlorobenzene, which gives,
NH:
1,3-dinitro-4-l3-aminoethylamino-benzene, which in turn
This compound is prepared by condensing chloroacet
gives the required compound when reduced with sodium
hydrosulphide.
amide with nitro-p-phenylene diamine in accordance with
The steps of the synthesis are represented in the fol- 45 the following scheme:
lowing:
NH;
NH-CH:—G O—NH2
Cl
———r
N0:
60
N 0,
NHz
(X)
N0:
(VII)
N0!
NH:
(XI)
Line of proceeding-Into a round ?ask equipped with
NO:
NH:
55 a mercury-sealed stirrer is introduced 0.8 mol. of nitro
p-phenylene diamine. 60 g. of calcium carbonate, 1
litre of hot water and 0.8 mol.+10% of chloroacetamide
are added, the carbon dioxide evolved being collected in
order to check the progress of the reaction. The re
action mixture is re?uxed for 31/2 hours, and is then ?l
N 0:
(VIII)
N03
(IX)
tered hot.
The resulting product is allowed to crystallize and is
washed again with water. A compound melting at 183°
C. is obtained. Yield: 60%.
Condensation.-Into a round ?ask equipped with a re
?ux condenser are introduced 150 g. of 97% pure ethyl 65 ‘ After crystallization from water, a violet powder melt
ene diamine and 9.5 g. of anhydrous cupric chloride. 0.6
mg at 190° C. and pointing to Formula X1 is obtained.
Analysis:
mol. Compound VII is gradually added. The tempera~
ture rises to 85° C. and is maintained at this level for
half an hour with heating. The solution is then poured
into 2 litres of ice-cooled water. The precipitate formed 70
is ?ltered, dissolved in 2 litres of water, ?ltered again,
pasted with a little water and then ?ltered again.
After the last ?ltering, the precipitate is dissolved in
300 ml. of boiling ethyl alcohol and ?ltered, and 10%
aqueous hydrochloric acid is added to the ?ltrate to form 75
Element
Calculated
percent '
Found
percent.
g....................................... ._
45. 71
4.76
45.64
4.87
N
26.66
26.89
-
Dyeing.—A 1% solution of 1-amino-2-nitro-4-N
3,049,393
5
6
acetarnidoaminobenzene is prepared and made weakly
alkaline with ammonia. This solution imparts a red tint
Dyeing test.—A dyeing test carried out under the same
conditions as with the preceding composition yielded com
to live or dead hair.
parable results.
The shade obtained is not sensitive
oxidizing agents such as for example, hydrogen peroxide.
EXAMPLE 4
5
1-N(Bem-Diethylamino-Ei/zyl) Nirr0-3-Diami1101,4-Bcnzene
EXAMPLE 6
1-N[(Beta-Diezhylamino-Ethyl) (Methyl)] Nitro-3
Dmmmo'l??enzme
(32H5
CQHS
NIr-oHQoIhN
_
CH3~N—CH2CH2N
|
10
\
C2Ha
C2115
—-N0:
No,
l
15
NH;
11111,
This product is prepared from nitroparaphenylene-
This?omposilion is Prepared from I-NQmethYU-HitI‘O
diamine, by condensation with the hydrochloride of beta-
3-dl?mlno-L4-Penlene by Cond?nsatlon W_lth hydrochlo
diethyl amino-chloro-ethane, in the presence of calcium
ride of beta-dlethyl-amino-chlofo'cthane 1? an aqueous
carbonate, in an aqueous medium, by re?uxing.
20 medium in the presence of an excess of calcium carbonate
A mixture of 15.3 grams (0.1 mole) of nitropara~
phenylenediamine, and 10 grams (0.1 mole) of calcium
by re?llXfIlg
_IT1 a mlxtllfe 0f 3-35 grams (0-05 H1016) 0f l-N(melhyl)
carbonate in 100 cc. of water, is heated to boiling for a
n1tr°—3 diamlno-L4-benlene, 7 grams (O-07 mole) 0f__¢a1
period of 35 minutes, 19 grams (0'11 mole) of hydro.
cium carbonate and 85 cc. of water, heated to boiling,
chloride of beta-diethylamino-chloro-ethane dissolved in 25 there is_ added drop by drop, Over a Perlod 0f 35 minutes,
50 cc_ of Water, is added drop by drop
a solution of 12.66 grams (0.07 mole) of the hydrochlo
After the carbon dioxide has ceased to be released, it
ride of beti1-diethyl-amino‘clllofp'ethane in 35 cc- of
is ?ltered and the excess of calcium carbonate is elim-
Water, to release the ¢_aTb_°n ‘lloxlde'
inated. After cooling, the hydrochloride of 1-N(beta-
_
Aftfir the Pal'boll dloxlfie 15 P0 longer ‘belng releatsed
diethylaminoethyl) nitro-3-diamino_Lmbenzene precipl; 30 the mixture is ?ltered at 1ts boiling temperature to elim
tates out in the-form of brownish red crystals.
Yield;
inate the excess of calcium carbonate. Then, after cool
7()%_
This hydrochloride when remwstalhzed from methanol,
ing, the ?ltrate is alkalized by adding ammonia. The
liberated base is extracted with ether and isolated in the
melts with decomposition at 180—182° C.
usual manner in the form of an'oil-
Analysis:
35
Element
Theory
Found
_
This base is then transformed into a hydrochloride by
passing gaseous hydrochloric acid into the methanol solu
tion. The precipitated hydrochloride is then ?ltered and
vacuum dried. There is thus obtained a yield of 60% di
0 ....................................... __
49. 91
49.19419. 45
N62355-
£1111: ----------------------- __________________________ n
'
'
chlorhydride of l-N[(beta-diethyl-amino-ethyl) (methyl)]
40 nitro-3-diamino-1,4-benzene which, when recrystallized
'
in methanol, melts with decomposition at 162-163" C.
Dyeing tesz‘.-—An aqueous, 1% solution of this com-
Analysis:
position brought to pH 7 by the addition of ammonia
was applied cold to white living hair and left in contact 45
therewith for ?ve minutes. The hair was dyed a very
Element
Theory
deep red violine shade.
Found
46.01
EXAMPLE 5
1-N(Beta-Dimethylamin0—Ethyl) Nitr0-3-Diamin0-
46. 20-45. 18
7. 07
7. 06-7. 16
111.51
16.64-16.85
50
1,4-Benzene
Dyeing test.—A 2% aqueous solution of this composi
CH3
tion, brought to pH 7 by addition of ammonia, applied
cold to white hair and left in contact therewith for
15 minutes, dyed the hair an intense violine shade.
/
NATCHiCH’N
OH“
55
_N02
EXAMPLE 7
1-N(Beta-Diethylaminc-Ethyl) Nitro-4-Diamin0
LIZ-Benzene
NH;
oil-I5
Under the same conditions as for the composition of 60
NIL-OHQCHQN/
l-N(beta-diethylamino-ethyl) nitro - 3 - diamino-1,4-ben-
C H
zene, by condensation of hydrochloride of beta-dimethylamino-chloroethane on nitroparaphenylenediamine a yield
of 50% chlorhydratc of l-N(beta-dimethylamino-ethyl)
nitro-3-diamino-1,4-benzene is obtained which, when recrystallized with methanol melts with decomposition at
2 5
205-208°
C.
r
‘’
,
‘N112
I
N01
_
Analysis:
Element
Theory
Found
_
,
_
_
,
_
Th1s compositlon is prepared by reducing with sodium
sul?de in a hydro-alcohol medium (beta-diethylamino
70 ethyl) dinitro-2,4-aniline. The latter product is obtained
in a known manner by condensing dinitro 2,4-chloroben
zene with N-N-diethyl-ethylenediamine.
42:23
“692E332;
To a solution of 42.5 grams (0.15 mole) of beta
2150
21-43'21-56
diethyl-amino-ethyl-dinitro-Z,4-aniline in 600 cc. in 95%
75 ethyl alcohol at a temperature of 95° there is added, drop
3,049,393
by drop, a solution of 21.5 grams (0.385 mole) of sodium
EXAMPLE 9
sul?de in 600 cc. of ethyl alcohol at 95° and 48 cc. of
1-N[ (Befa-Diethylaminoethyl) (Ethyl) ] Nitr0-3 -
water over a period of an hour and a half.
Diamin0-1,4-Benzene
The alcohol is evaporated under a vacuum and the sul
?de is dissolved in 209 cc. of 10% hydrochloric acid.
The solution is ?ltered and 42.5 cc. of 20% ammonia is
added at a temperature below 20° C.
solution obtained is about 7.
The pH of the
The monochloride precipitates and when recrystallized
from alcohol melts with decomposition at 210° C. Yield: 10
80%.
NO:
IllH:
By dissolving this hydrochloride and alkalizing it with
sodium hydroxide in an aqueous solution, the correspond
ing base may be obtained after cooling, which base when
recrystallized from benzene, melts at 62° C.
This product is prepared from 1-N(ethyl) nitro-3-di
amino-1,4-benzene by condensation with beta-diethyl
amino-chloro-ethane.
Analysis:
In a mixture of 9.05 grams (0.05 mole) of 1-N(ethyl)
nitro-3-diamino-1,4-benzene, 4 grams (0.04 mole) of
calcium carbonate and 80 cc. of water, there is added, as
,
Calculated at
Element
CIZHMN‘O2
Found
20 it boils, 13.32 grams (0.077 mole) of beta-diethylamino
chloro-ethane in 35 cc. of water (duration of addition:
C. ....................................... ..
H _______________________________________ -.
57. 15
7. 94
57. 38-57. 15
8. 01-7. 87
N _______________________________________ __
22. 21
21.80-21.85
2 hours).
The mixture is cooled and extracted with methyliso
butyl-ketone to remove any 1-N(ethyl) nitro-3-diamino
25 1,4-benzene which has not been transformed. The mother
liquors are then alkalized by using 40% sodium hydroxide.
Extraction by ether follows, and after conventional treat
ride of this composition was brought to pH 7 by adding
ment a violet oil is obtained. This product when puri?ed
ammonia, and applied cold to grey hair, and after a con
by passing its methyl alcohol solution over alumina, al
tact of 15 minutes produced a bright yellow shade.
30 ways yields an oil after evaporation of the methyl alco
hol. Yield: 75%.
EXAMPLE 8
Analysis:
Dyeing test.—-An aqueous solution of 1% hydrochlo
1-N( Gamma-Diethylamino-Propyl) Nitro-3-D iam ino
Element
1,4-Benzen‘e
Theory
Found
35
0 ....................................... .H _______________________________________ __
N
40
60. 00
8.57
20. 00
60-55-60. 32
9.00-9.58
19. 52-19. 69
An aqueous 1% solution of 1-N[(beta-diethylamino
ethyl) (ethyl)] nitro-3-diamino-1,4-benzene, adjusted to
a pH of 7, is applied cold to white hair and allowed to
NO:
remain in contact therewith for a period of 15 minutes
and produces a rose-beige tint.
NB:
This application is a continuation in part of applica
This product is prepared from nitroparaphenylene
diamine by condensation with gamma-diethyl-amino 45 tion Serial No. 624,227, ?led November 26, 1956, now
abandoned.
chloro-propane in an aqueous medium, by re?uxing.
A mixture of 11 grams (0.072 mole) of nitropara
phenylene-diamine, 10.75 grams (0.072 mole) of gamma
What is claimed is:
1. A composition for dyeing animal ?bres which com
prises an alkaline solution of a nitro phenylenediamine
diethyl-amino-chloro-propane, and 80 cc. of water is
50 compound selected from the group consisting of 2-nitro
heated by re?uxing for 2 hours.
1,4-phenylenediamine and 4-nitro-1,2-phenylenediamine
The mixture is cooled and the nitroparaphenylene
in which the amino group furthest from the nitro group is
diamine which has not reacted is ?ltered. The ?ltrate is
a group having the formula
made alkaline by adding an aqueous sodium hydroxide
solution, and is then extracted with ether.
After conventional treatment an oil is obtained which 55
is transformed into a hydrochloride by passing aqueous
hydrochloric acid into a solution of this product in
ethanol. There is thus obtained a yield of about 70%
in which R1, R2, and R3 each represent a substance se
lected from the group consisting of hydrogen atoms and
alkyl radicals from 1 to 3 carbon atoms, m represents an
integer from 2 to 4 and n is equal to 0 or 1.
of the dichlorhydride of 1-N(gamma-diethyl-amino
2. A method of dyeing animal ?bres which consists in
60
propyl) nitro-3-diamino-1,4-benzene which when recrys
applying thereto an alkaline solution of a nitro phenylene
tallized is absolute ethanol and melts with decomposition
diamine compound selected from the group consisting of
at 160° C.
2-nitro-1,4-phenylenediamine and 4-nitro-1,2-phenylene
Analysis:
diamine in which the amino group furthest from the
65 nitro group is a group having the formula
Element
Theory
46. 1
7. O8
16. 51
Found
45. 50-45. 43
7. 09-6. 93
15 78—16. 30
in which R1, R2 and R3 each represent a substance selected
from the group consisting of hydrogen atoms and alkyl
70 radicals from 1 to 3 carbon atoms, m represents an integer
from 2 to 4, and n is equal to 0 or 1.
3. A composition for dyeing animal ?bres which com
prises an alkaline solution of 1-amino-2-nitro-4-(yo-amino
ethyl) amino benzene.
applied cold to white hair and left in contact therewith
75 4. A composition for dyeing animal ?bres which com
for 15 minutes and produces a violine red shade.
An aqueous 1% solution of the hydrochloride of said
composition, brought to pH 7 by adding ammonia, is
3,049,393
10
prises an alkaline solution of 1-nitr0-3-amino-4-(?-amino~
ethyl) amino benzene.
-
prises an ‘alkaline solution of 1-N(g-amma-diethylamino~
propyl) nitro-3-diamino-1,4-benzene.
11. A composition for dyeing animal ?bres which com
5. A composition for dyeing animal ?bres which com
prises an alkaline ‘solution of 1—N[(beta-diethylamino
prises an alkaline solution of l-amino-2-nitro-4-(N-acet
5 ethyl) (ethyl)] nitro-3-diamino-1,4-benzener
amido)~amino benzene.
6. A composition for dyeing animal ?bres whichycom
References Cited in the ?le of this patent
prises an alkaline solution of _1-N\(beta-diethylamino
UNITED STATES PATENTS
ethyl) nitro-3-diamino-1,4-benzene.
7. A composition for dyeing animal ?bres which com
1,932,901
Lehmann _____________ __ Oct. 31, 1933
prises an alkaline solution of 1-N(beta-dimethylamino 10 2,618,657
Vaughn _____________ .._ Nov. 18, 1952
ethyl) nitro-3-diamino-1,4-benzene.
8. A composition for dyeing animal ?bres which com
2,750,326
Eckardt __r ____________ __ June 12, 1956
1,051,605
France _______________ __ Ian. 18, 1954
FOREIGN PATENTS
prises an alkaline solution of 1-N[(beta-diethylamino
ethyl) (methyl)] nitro-S-diamino-1,4-benzene.
9. A composition for dyeing animal ?bres which com 15
prises an alkaline solution of l-N(beta-diethylamino
ethyl) nitro-4-cliamino-1,2-benzene.
10. A composition for dyeing animal ?bres which com
4
OTHER REFERENCES
Weissberger: Abstract from 0.6., vol. 652, pp. 289-290,
November 6, 1951.
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